Unsaturated sulfone amines



United States Patent US. Cl. 260584 2 Claims ABSTRACT OF THE DISCLOSURE Unsaturated sulfone compounds corresponding to the structure (CH =CHSO CH CH OC,,H EN

wherein a has a value of 1 to 8. The compounds can be used for the chemical modification, particularly cross-linking, of polymers containing active hydrogen atoms.

The present application is a divisional of application Ser. No. 107,893, filed May 5, 1961.

The present invention relates to new unsaturated sulfone compounds and methods of preparation thereof. It also relates to the products resulting from the reaction of the sulfone compounds of the present invention with polymeric materials, and methods of preparing said reaction products.

It is known that unsaturated sulfones, such as divinyl sulfone, are useful in enhancing the properties of natural and synthetic polymers containing active hydrogen atoms. Examples of such polymers include cotton, rayon, wool, polyvinyl alcohol, starch, and the like. The use of divinyl sulfone on an industrial scale for such purpose has been limited due to objectionable physicochemical and physiological properties of this reagent. For example, divinyl sulfone is extremely toxic to humans not only if ingested but also by simple absorption through the skin. In addition the compound is a strong lachrymator and vesicant. It is also difficult to handle because of its relatively high vapor pressure. Moreover, at alkaline pH, particularly 9.0 and above, divinyl sulfone reacts readily with water so that aqueous alkaline solutions of divinyl sulfone have limited stability. Accordingly it is highly desirable to provide sulfones which are free of the aforementioned objections and yet are capable of imparting valuable properties to natural and synthetic polymers containing active hydrogen atoms and particularly to fiber forming polymers.

It is, therefore, an object of this invention to provide novel unsaturated sulfones which enhance the properties of polymers containing active hydrogen atoms and yet are nonirritating, odorless, and have a low vapor pressure.

A further object of this invention is to provide novel unsaturated sulfones which are relatively stable and resistant to self condensation and polymerization.

A further object of this invention is to provide a novel process whereby the unsaturated sulfones of this invention are reacted with polymers containing active hydrogen atoms so as to impart valuable properties thereto such as increased resistance to water, dimensional stability, and when the polymer is in the form of a fabric, improved wet and dry crease recovery.

A further object of this invention is to provide novel products which result from reacting the sulfones of this invention with polymers containing active hydrogen atoms.

These and other objects will be apparent from the description which follows.

Patented Sept. 8, 1970 The novel sulfone compounds of this invention correspond to the structure:

where n is an integer number and has a value of 2 to 3: A is selected from the group consisting of oxygen and nitrogen, and does not have any hydrogen atoms attached to it; R is a lower alkyl group; Q is an organic radical in which the number of unsatisfied valences is equal to n, and b has a value from 0 to l but if A is oxygen, then b is O.

The novel process of this invention including the novel products formed therefrom comprises reacting the compounds of Formula I above with polymers containing active hydrogen atoms in the presence of an alkaline catalyst at temperatures varying from ambient (e.g., 20 C. to 25 C.) to 200 C.

Included among the compounds of Formula I above are, for example, the following:

11 cn cnso cn cn m o where n has a value from 2 to 3 and Q is a radical selected from the group consisting of wherein a has a value from 1 to 8; and

( a 2 a) Z wherein a has a value from 1 to 8 and R is an alkyl group.

(III) CH2=GHSO2CH2CHzN 2Q where R is a lower alkyl group, b has a value from 0 to 1, and Q is a bivalent organic radical selected from the group consisting of the acyclic radicals wherein X is selected from the group consisting of oxygen and sulfur, and

wherein a has a value of 2 to 10.

Compounds contemplated by Formula 11 include those of Formulas IV, V, and VI as follows:

II III where R is a bivalent organic radical and R and R are lower alkyl groups. In the foregoing formula, the group can be the residue of a his secondary amine,

III

where Y is part of a heterocyclic ring of which the two nitrogens are also a part.

(VIII) where R is a lower alkyl.

The sulfone compounds of Formula I can be prepared by the addition of divinyl sulfone to polyfunctional hydroxyl, amino, amido and thioamido compounds of suitable structure using at least two mols of divinyl sulfone for each mol of hydroxyl, amino, amido or thioamido compound.

For example, the product of Formula II where a=2 can be prepared from three mols of divinyl sulfone and one mol of triethanolamine. The product of Formula III where a is 2 and R is methyl can be prepared from two mols of divinyl sulfone and one mole of N-methyl diethanolamine. Similarly, the product of Formula IV is obtained from a 2/ 1 mol ratio of divinyl sulfone to piperazine, and the products of Formula V can be obtained from a 2/1 mol ratio of divinyl sulfone to a bis-secondary amine. In all instances, a larger excess of divinyl sulfone can be used for the synthesis and later removed by distillation, but at least two mols of the divinyl sulfone must be used in order to avoid the formation of polymeric materials and saturated byproducts.

The reactions employed for the synthesis of the new sulfone compounds can be represented by a generic Equation 1 nCHz=CHSOzGH=CHz+ Q AH in which n, b, A, R and Q have the same meaning as in Formula I.

The conditions under which reaction (1) takes place depend greatly on the structure of the groupings A and Q.

Basic compounds (compounds Q,

in which amino groups are present) react readily at room temperature in the absence of a catalyst. Neutral compounds on the other hand add to the divinyl sulfone to give the desired products only in the presence of alkaline catalysts and at elevated temperature. The presence of solvent is not essential, but often desirable in order to facilitate the control of temperature during the reaction and the isolation of the reaction products.

The new sulfone compounds of the present invention, as represented by Formula I, have the following important structural features:

(a) They contain at least two vinyl sulfone groupings SO CH=CH which are capable of addition to compounds containing active hydrogen in the presence of catalytic amounts of alkaline materials.

(b) They do not contain active hydrogen atoms in the molecule and are not prone to self condensation and polymerization.

(c) They are solids or liquids of very low vapor pressure, odorless and nonirritating (in contrast with divinyl sulfone itself).

(d) They are stable to hydrolysis in neutral, acidic and weakly alkaline aqueous solutions.

Due to these properties, the sulfones are desirable reagents for the chemical modification, and more specifically for the cross-linking of polymers containing active hydrogen atoms. The reaction products of the new sulfones with textile fibers are particularly important and exhibit many desirable properties. It is known that the properties of textile materials can be enhanced by crosslinking reactions. The dimensional stability, resilience, water resistance, and flat drying properties can be improved by cross-linking treatments and many processes are known by which cross-linking can be achieved. By the use of the new sulfones, products of outstanding properties can be obtained under practical conditions, and the disadvantages of known processes can be minimized.

The processes by which polymers containing active hydrogen atoms, and more particularly textile materials can be treated with the new sulfones, consist of alkali catalysed reactions in which cross-linking takes place by addition of the vinyl groups to the active hydrogen atoms of the polymer. These reactions can be carried out at temperatures from ambient temperature to 200 C., depending on the amount and basic strength of the alkaline catalyst. They can be carried out in the presence or in the absence of water or solvent, and the preferred conditions for the reaction are generally dictated by the specific polymer being reacted. When the polymer has a tendency to be degraded by strong aqueous alkaline solutions, as for example in the case of wool fiber, weakly alkaline catalyst are preferred. When the polymer is not attacked by alkali, strong bases can be used to achieve rapid reaction at low temperature.

The hydroxides, phosphates, carbonates, bicarbonates, silicates and acetates of alkali metals are suitable catalysts for the reactions. Quaternary ammonium hydroxides and other nonvolatile organic bases can also be used.

The reaction products obtained from the polymer and the novel sulfones of Formula I are new polymeric products formed in accordance with a generic Equation 2.

PolCHzCHzS OzCHzCHzl? Qxll CHzCHzSOzCHzCHzPol Rb Rb in which A, R b and Q have the same meaning as in Formula I, n is 2 and PolH is used to designate a polymer molecule containing active hydrogen atoms.

When the active hydrogen atoms of the polymer are part of hydroxyl groups, as for example in the case of cellulose, the products formed contain ether groupings as shown in Equation 3.

OellO CHzCHzS OzOHzCHzAQ A CHzCHzSOzCHzOHzO Cell Rb R in which CellOH is used to designate a cellulose molecule.

The properties of the new cross-linked polymeric products depend in part on the amount and structure of the cross-linking agent employed for their prepartion, and especially on the structure of the groupings A and Q. Some of these properties will be illustrated by the examples which follow.

EXAMPLE I OIL-CH2 One mole of divinyl sulfone (118 g.) and 350 ml. ether were placed in a 3-neck flask. To this was added dropwise, with stirring and cooling to between 2030 C., a solution of 0.5 mole (43 g.) of piperazine in 43 g. methanol (preheated to 40-50 C. to dissolve).

The solution of piperazine in methanol was added over a 30-minute period. The resulting slurry of white crystals in ether was filtered, and the filter cake washed with ether and dried of solvent in a desiccator. This preparation gave an 88% yield. A preparation in which 7 mols of divinyl sulfone were reacted with 3 mols of piperazine by the same procedure, gave a 92% yield. When the ether was replaced with benzene, the yield of product was only 37% of the theoretical.

The percent sulfur content of the product of Example 1 was 19.96% (theory: 19.86%). The melting point of the product of Example 1 was 115 -117 C. The prodnot was a white crystalline solid, moderately soluble in water and very soluble in acetone and acetone-water mixtures.

The dihydrochloride of the product could be easily prepared by addition of anhydrous HCl to a solution of the material in inert solvent. The percent chloride of the dihydrochloride was 17.3% (theory=17.9%).

EXAMPLE 2 The product of Example 1 was also prepared by the following procedure-3 moles of divinyl sulfone (354 g.) were dissolved in 1062 g. of a 4:1 dioxanezwater mixture (by weight), in a 3-neck flask. To this was added, slowly, with agitation, and cooling to below 40 C., a solution of 1.5 moles (129 g.) of piperazine in 387 g. of the same solvent mixture. The piperazine solution was added over a period of 30 minutes. The solution so obtained contained 25 of the desired product. It was clear yellow and remained clear even after storing at room temperature for a month.

1 mole 118 g.) of divinyl sulfone and 300 ml. of dioxane were placed in a 3-neck flask and heated to reflux. To this was added, dropwise, with stirring, a solution of 1 g. metallic sodium, 0.5 mole dibutylthiourea (94 g.) in 100 g. of dioxane. The dibutylthiourea solution was added during a period of 2 hours, and the solution was refluxed for an additional four hours after completing the addition. The reflux temperature was from 103 -106 C. The preparation was stripped of solvent from 32% solids to 89% solids at a maximum pot temperature of 112 C. at 25 mm. The vinyl content of the residue (determined by analysis using the method based on addition of lauryl mercaptan) was 11.8% (theory 11.3

EXAMPLE 4 CHz=OHS OzOHzCHzN-C O-N-CHzCHzSOzCH -CH2 5 moles of divinyl sulfone (590 g.) and 300 g. of dioxane were placed in a flask and heated to refluxing. In a separate flask, 1 gram metallic sodium was dissolved in a solution of 0.5 mole (44 g.) of dimethylurea in 100 g. of,.dioxane'(heated to dissolve). The latter solution was added dropwise, with stirring, to the former over an interval of 45 minutes. The reflux temperature was 116 C. The total solids content after completing the addition was 15.7%.

After completing addition of the dimethylurea solution, the clear solution was refluxed for 5 hours. The preparation was then stripped to maximum pot temperature of 121 C. at 25 mm. to remove solvent and excess divinyl sulfone. The residue so obtained, consisting of crude product contained 18% vinyl groups (determined by analysis with mercaptan), while the calculated vinyl content was 16.7%. The crude product was a semi-crystalline mass which could be purified by crystallization.

EXAMPLE 5 N (CH CH OCH CH SO CH=CH 3 3 moles of divinyl sulfone (354 g.) and 700 g. of dioxane were placed in a 3-neck flask and heated to refluxing. In a separate flask, 0.075 mole of metallic sodium (1.7 g.) were dissolved in a solution of 1 mole triethanolamine (149 g.) in 100 g. dioxane (heated to accelerate solution). The latter solution was added dropwise to the former, with agitation, during an interval of 1 hour. Total solids=38.6%. The reflux temperature was 103 -107 C. At this point, the solution contained a small quantity of solids which were filtered off. No further precipitation occurred in the filtrate on standing. The vinyl content (determined by the mercaptan method) gave 5.7% vinyl for this solution. The reaction mixture was stripped of solvent under reduced pressure. The residue, containing 100% solids, had a vinyl content of 13.75%. (Theory for 100% solids at 100% reaction=16.l%; theory for 100% solids at 0% reaction=32.2% vinyl.) The crude product was a viscous syrupy liquid.

EXAMPLE 6 A sample of cotton fabric X 80 print cloth) was impregnated on a laboratory padder with the 25% solution prepared as described in Example 2. The wet pickup was 80%. The fabric was dried, then padded with a 0.5% sodium hydroxide solution and allowed to stand at room temperature wet for 1 hour. After neutralizing and washing, the fabric exhibited excellent crease recovery and fiat drying properties. The weight increase of the fabric was 8.5%, indicating that 42% of the sulfone ap plied had reacted with the cotton. The nitrogen and sulfur analyses of the treated cotton fabric confirmed these values. The physical properties of the treated fabric were as follows:

Crease recovery, degrees Warp tear(=) strength, lbs. Wet Dry Example 6 1. 4 282 218 Untreated control 1. 6 149 162 Tested by the Elmendorf method (ASTM D-1424-59). Tested by the Monsanto method (AATCC 66-1959) expressed as the sum of results obtained in the warp and filling directions.

ties, and it is believed to be due to the chemical structure of the sulfone employed.

When the procedure of Example 6 was repeated using a solution of the sulfone of Example 2 which had been diluted to 12% with water, the following results were oblose and the sulfone. The analysis of the treated fabric for sulfur and nitrogen gave results which were consistent with the weight increase observed. The ratio of sulfur to nitrogen in the treated fabric was 1:82 (calculated 64/282.3). The performance of this treated fabric was mined, 5 outstanding; the fabric had excellent flat drying proper- The w t pickup wa 90%. The weight increase for the ties and dimensional stability, the physical properties, and treated fabric was 5.3%, indicating that a 49% yield of particularly the wet properties, were greatly improved the reaction product with the sulfone was obtained. The by the treatment without the serious losses in abrasion rewet crease recovery of the treated cotton was 254 (comsistance which are generally encountered when regenerpared to 149 for the untreated control). ated cellulose fabrics are treated with cross-linking agents.

Wet tensile Wet tear b strength, lbs. strength, lbs. Wet crease e Flex abrasion Warp Fill Warp Fill recovery, degrees cycles (warp) Examplet) 28 40 1.5 2.2 266 820 Untreated control- 26 31 l. 6 1. 7 154 1, 500

u Ravel strip methodASTM D-39-59.

b Elmendorf method-ASTM D-1424-59.

u Monsanto method-AATOC 66-1959.

d lb. head, 2 lbs. toggle-ASTM D-l175-55'I.

The nitrogen content, sulfur content and physical properties of the treated fabrics were unchanged after repeated launderings.

EXAMPLE 7 A cotton fabric (80 x 80 print cloth) was impregnated on a laboratory padder with a solution containing 100 grams per liter of the crystalline product of Example 1 and grams per liter of potassium bicarbonate (dissolved in a 2 to 1 mixture of water and acetone). The wet pickup was 82%. The fabric was framed to the original dimensions, dried, then heated in a curing oven at 150 C. for 2 minutes, then washed thoroughly and dried. The weight increase was 8.3%, indicating that a quantitative yield had been obtained in the reaction between the cotton celulose and the sulfone. The physical properties of the treated fabric were excellent, and remained unchanged after a large number of launderings in 'a home type automatic washer.

Crease recovery, degrees 0) Tested by the ravel strip method (ASTM D-39-59). Tested by the Monsanto method (AATCC 661959) expressed as the sum of results obtained in the warp and filling direction.

EXAMPLE 8 A sample of wool flannel was treated with a solution prepared by diluting the product of Example 2 with water to a concentration of 12.5% sulfone and adding 10 grams per liter of anyhydrous potassium carbonate. The fabric was treated on a laboratory padder, adjusting the pressure of the rolls to obtain a 95% wet pickup. The treated fabric was framed to the original dimensions, dried, then heated in a curing oven at 120 C. for minutes. The wool fabric was then thoroughly rinsed and dried. On washing in a home type automatic washer at 4050 C., the treated fabric did not shrink or felt appreciably, while the area shrinkage of the untreated control sample was 8%. The tensile strength of the wool fabric was not decreased by the treatment, in contrast with shrinkproofing treatments commonly employed for W001 fabrics, which are known to impair the tensile strength severely.

EXAMPLE 9 A spun rayon fabric was impregnated on a laboratory padder with the solution prepared in Example 2 to 90% wet pickup and dried. After drying, the sample was padded with a solution containing 5 grams per liter of sodium hydroxide, and allowed to stand wet at room temperature for 30 minutes. It was then neutralized, washed and dried. The weight increase was 16%, indicating a 70% yield in the reaction between the regenerated cellu- The warp shrinkage of the treated fabric after 10 launderings was 2.5%, while the warp shrinkage of the 5 untreated control fabric was 17.5%

EXAMPLE 10 (A) A sample of spun rayon fabric was impregnated on a laboratory padder with a solution containing 200 grams per liter of the crystalline product of example 1 and 50 grams per liter of anhydrous potassium bicarbonate. The wet pickup was 94%. The fabric was framed to original dimensions, dried and heated in a curing oven for 2 minutes at 150 C. It was then rinsed thoroughly and dried. The weight increase obtained was 15.7%, corresponding to an 83% yield of the desired product. The crease recovery of the treated fabric was greatly improved, as shown by the following results:

Crease recovery Dry Wet Example 10(A) 258 203 Untreated control 185 139 Crease recovery, Dry tensile Wet tear degrees strength a strength b warp, lbs. warp, lbs. Dry Wet Example 10(B).-..- 68 2. 4 233 247 Untreated control. 61 1. 9 188 228 B Ravel strip methodASTM D-39-59. b Elmendorf meth0dASTM D-1424-59. Monsanto method-AATCC 664959.

EXAMPLE 11 A cotton fabric x 80 print cloth) was treated on a laboratory padder with a solution prepared by dissolving 200 grams of the product of Example 3 in 400 grams of acetone and adding 400 grams of water. The wet pickup was 60%. The fabric was dried, then treated with a 2% solution of sodium hydroxide and allowed to stand at room temperature wet for 1 hour. It was then washed and dried. The weight increase was 6.2%, indicating a 52% yield of the desired product. The wet crease recovery of the treated fabric was 236, compared with for the untreated control fabric.

9 EXAMPLE 12 ing to an 8.5% weight increase). The treated fabric ex- 5 hibited excellent properties, particularly with regard to crease recovery, flat drying, 'water resistance, and dimensional stability. For example, the thread count of the untreated fabric increased from (71 x 66) to (76 x 71) after ten launderings indicating substantial shrinkage, while the thread count of the treated fabric remained unchanged in the course of the ten launderings. The wet tensile strength of the untreated fabric in the warp direction decreased from 26 lbs. to 17 lbs. after 10 launderings and the dry warp tensile strength decreased from 46 lbs. to 33 lbs. The warp tensile strength of the treated fabric on the other hand (27 lbs. wet and 42 lbs. dry) remained unchanged after 10 launderings.

We claim:

1. An unsaturated sulfone compound corresponding to the structure (CH =CHSO CH OC H 3 E N wherein a has a value from 1 to 8.

2. The compound corresponding to the structure:

N (CH CH OCH CH SO CH=CH 3 References Cited UNITED STATES PATENTS 3,277,084 10/1966 Martin.

CHARLES B. PARKER, Primary Examiner L. RAYMOND, Assistant Examiner US. Cl. X.R. 

